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United States Patent 2,855,392 COBALTIFEROUS AZO-DYESTUFFS Arthur Buehler, Rheinfelden, and Christian Zickendraht, gen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm N0 Drawing. Application September 2, 1954 Serial No. 453,932

Claims priority, application Switzerland September 8, 1953 10 Claims. (Cl. 260-145) This invention relates to cobaltiferous azodyestuffs and a process for their manufacture.

The invention is based on the observation that valuable, new cobaltiferous azo-dyestufis are produced, which contain one atom of cobalt in complex combination with two molecules of different monoazodyestufis, when agents providing cobalt are reacted upon mixtures of an 'free from water-'solubilizing substituents and which couples in o-position to the amino group. The specified coupling can take place by conventional methods, preferably in an acid or neutral medium.

There are suitably used as o-hydroxydiazo-compounds, diazo-compounds of such o-hydroxyamines of the benzene series of which the benzene nuclei contain in addition to the hydroxyl and the amino group also further substituents, such as halogen atoms (for example chlorine), alkyl groups (for example methyl), alkoxy groups (for example methoxy), acylamino groups or preferably nitro groups.

As examples of such o-hydroxyamines there may be mentioned: 4-methyl-, 4-methoxyand 4-chloro-2-aminol-hydroxybenzene, 4:6-dichloro-2-amino-l hydroxybenzene, 4-methyl-5- or -6-nitro-2-amino-l-hydroxybenzene, 4-chloro-5- or -6-nitro-2-amino-l-hydroxybenzene and especially 4-nitro-6-chloro-2-amino-l-hydroxybenzene, 6- nitro-4-acetylamino-2-amino-l-hydroxybenzene, 4-nitro-6- acetylamino-Z-amino 1 hydroxybenzene, 41-6 a dinitro- Z-amino-l-hydroxybenzene and primarily 4-, 5 0r 6 nitro-2-amino-l-hydroxybenzene.

As coupling components are especially useful naphthylamines free from solubilizing groups which are capable of coupling in o-position to the amino group. As examples there may be mentioned: 2-phenyland 2- methylarninonaphthalene, 6-bromoand 6-methoxy-2- aminonaphthalene, 6-methyl-2 aminonaphthalene and primarily Z-aminonaphthalene itself. Instead of this latter component, Z-aminonaphthalene-l-sulfonic acid can also be used, since this acid couples in l-position with splittingofi of the sulfonic acid group and therefore leads to the same starting dyestuffs as Z-amino-naphthalene itself.

1 The o:o'-dihydroxy-monoaz-o-dyestuffs which are used together with the o-hydroxy-o amino monoazo dyestufis just mentioned for the preparation of the mixture used as starting materials in the present process, can be produced from dyestufi components containing sulfonamide or sulfone groups and which are free from sul- 2,855,392 Patented Oct. 7, 1958 tonic acid and carboxyl groups, as for example by coupling an o-hydroxydiazo-compound of the benzene series with a compound which couples in the adjacent position to a hydroxyl group or an enolizable keto-group, in which case the coupling component and/or with advantage the diazo component can contain a sulfonamide or a sulfone group, for example a phenyl or methyl sulfone group. Of especial value have proved the dyestuffs containing at least one sulfonamide group.

As o-hydroxydiazo-compounds for the preparation of these dyestuffs those are useful, for example, as have been mentioned above for the preparation of the o-hydroxy-o-amino-dyestuffs. These diazo-compounds which are free from sulfonamide and sulfone groups are only to be coupled with azo components which contain a sulfone or a sulfonamide group. Especially good results are obtained with diazo-compounds of amines containing sulfone or sulfonamide groups, as for example the diazocompounds of 2-amino-1-hydroxybenzene-4- or -5-sul fonamide, of 6-nitro 2 amino l hydroxybenzene-4- sulfonamide, of 4chloro-2-amino 1 hydroxybenzene- S-sulfonamide, of 6-chloro-2-amino-l-hydroxybenzene- 4-sulfonamide Or of 4-nitro-2-amino-l-hydroxybenzene- 6-sulfonamide or of the corresponding N-arylor N- alkyl-substituted sulfonamides; moreover with diazocompounds from Z-amino-1-hydroxybenzene-4- or -5- methyl sulfone, 4-chloro-2-amino 1 hydroxybenzene- 5- or -6-methyl sulfone, Z-amiuo-l-hydroxybenzene-4- or -5-phenylor -benzyl sulfone.

As examples of suitable coupling components of the specified type there may be mentioned: Compounds with phenolic hydroxyl group, such as p-substituted hydroxybenzenes, for example, 4-methyl-l-hydroxybenzene, 4- isopropyl-l-hydroxybenzene, 4-tertiary amyl-l-hydroxybenzene, 2:4- or 3:4-dimethyl-1-hydroxybenzene, 4-acety1- amino-3-methylor 4-methyl-2-acetylamino-1-hydroxybenzene, 4-acetylamino-l-hydroxybenzene, furthermore hydroxynaphthalenes as for example 1-benzoylamino or 1-acetylamino-7-hydroxy-naphthalene, l-n-butyrylamino- 7 -hydroxynaphthalene, 1 carbomethoxyamino-7-hydroxynaphthalene, Z-hydroxynaphthalene, 6-bromoor '6- methoxy-Z-hydroxynaphthalene, S-chloro or 5:8-dichlorol-hydroxynaphthalene, 1-hydroxynaphthalene4- or -5- sulfonamide, 2-hydroxynaphthalene-6-sulfonic acid-N- methyl-N-fl-hydroxyethylamide, 2-hydroxynaphthalene-6- sulfonamide, hydroxquinolines, barbituric acids or pyrazolones, as for example 1-phenyl-3-methyl-5-pyrazolone, 1- (2-, 3- or 4'-chloropheny1)-3-methyl-5-pyrazolone, 1- phenyl-3-methyl-5-pyrazolone-3-sulfonamide, 1 phenyl- 3-methyl-5-pyrazolone-3-or 4-sulfonic acid methylamide, 1:3-diphenyl-5-pyrazolone, 2:4-dihydroxyquinoline, 5- chloro-8-hydroxyquinoline and primarily compounds which contain a carbon atom which is capable of coupling in an open chain, especially fi-ketocarboxylic acid derivatives, for example acetoacetic acid-isopropyl ester but preferably fi-ketocarboxylic acid arylamides, as for example acetoacetanilide, acetoacetic acid-o-, -m or -pchloranilide, 1-acetoacetylaminobenzene-3- or -4-sulfonamide, 1-acetoacetylaminobenzene-2-, -3- or -4-methyl sulfone, 1-acetoacetylaminobenzene-3- or -4-sulfonic acid methylamide.

In this case also the coupling can take place by conventional methods, for example in an alkaline medium.

In carrying out the process it is to be recommended in general to use for a mixture of about one molecular proportion each of two difierent dyestuiis of the specified type, about one gram atom of cobalt contained in a corresponding quantity of an agent providing cobalt, and/or to carry out the metallization in a medium within the range from faintly acid to alkaline. Of good suitability for carrying out the process are, for example, complex 3 cobalt compounds of aliphatic o-hydroxyor dicarboxylic acids which contain the cobalt in complex combination. In general, however, there are used simple salts of divalent cobalt such as cobalt sulfate or acetate or, if desired,

freshly precipitated cobalt hydroxide.

The conversion of the dyestuffs into the complex cobalt compounds takes place with advantage in the hot, in an open vessel or under pressure, if desired in the presence of suitable additions, for example in the presence of salts of organic acids, of bases, organic solvents or further agents which promote the complex formation.

The products obtainable according to the specified process are new. They are complex cobalt compounds which contain one atom of cobalt in complex combination with two molecules of difierent monoazo-dyestufis of which one constitutes an o-hydroxy-o'-amino-monoazodyestufi which is free from water-solubilizing groups, while the other is an o:o'-dihydroxy-monoazo-dyestuff which is free from sulfonic acid and earboxyl groups and contains as water-solubilizing grounp at least one sulfonamide or a sulfone group or both, for example one SO C H and one SO NH group.

Mixtures of such cobaltiferous mixed complexes can be prepared by the above specified process by reacting agents providing cobalt of the specified type upon two or more of the above-defined dyestufi mixtures at the same time, or by reacting simultaneously one cobaltiferous lzl-complex with two or more metal-free dyestuffs or also two or more metalliferous 1:1-complexes with one metal-free dyestutf in suitable quantity proportions.

The new cobaltiferous mixed complexes obtainable according to the above process are soluble in Water. They are suitable for the dyeing and printing of a variety of substances, primarily for the dyeing of animal materials such as silk, leather and especially wool or also for the dyeing and printing of synthetic fibers from superpolyamides and superpolyurethanes. They are primarily suitable for dyeing from a weak alkaline, neutral or weakly acid bath. Wool dyeings thus'obtained are distinguished by their uniformity, their purity and good fastness to light and also by a very good fastness to washing, fulling and rubbing.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relation between part by weight and part by volume being the same as that between the kilogram and the liter.

Example 1 3.08 parts of the dyestuff from diazotized S-nitro-Z- amino-l-hydroxybenzene and 2-aminonaphthalene are dissolved in 300 parts of Water at 80 C. together with 4.25 parts of the dyestufi from diazotized Z-amino-l-hydroxybenzene-4-sulfonic' acid methylamide and 1-acet0- acetylamino-Z-chlorobenzene, parts by volume of 2 N-sodium hydroxide solution being added. 20 parts of a solution of cobalt sulfate with a cobalt content of 3.25% are added and stirring is carried out for /2 hour at 85 C. When the metallization is complete the dyestufl is separated by addition of sodium chloride and neutralization with acetic acid and is filtered and dried. It forms a green powder which is soluble in water with a green color and in concentrated sulfuric acid with a brown color and dyes wool from a weakly alkaline, neutral or weakly acid bath in full green tints of good fastness properties.

In the following table there are listed further complex cobalt compounds which were obtained according to the above process. In columns I and H there are set out the two monoazo-dyestufis which are in complex combination with the cobalt atom and in column III the color of the tints obtained on dyeing parts of wool with 2 parts of the corresponding'cobalt compound from an acetic acid bath.

1 u in OH NH; on I o1 1 1 \1'=N N=N-CH-CONH green.

b0 NO OH; H; ombrr 011 NH, 011 g or 2..-- N N=N-CH-C ONE-O green.

N0 430 Hg o cm 0H NH, HO OH -N 3..-. N=N olive.

N=N -O\ 0M N0 C=N on NH, 0H 6 4. N--N 01 01mm I H m OH NH: HO

i 3 N= I alive.

N=NC I N0 1 (JHg OH NH, OH HO 6...- blueviolet 0H NH: OH B0 C1 7.... N: N=N-- blue.

OH NH: OH HO 3...- N=N N=N blue.

I 1 SOQNHCHI OH NHq OH OH 9-.-. H.N-0is-@-N=N- grey-olive.

OH NH: OH HO 1o.- N=N N=N m 1511 hue violet.

OzN- v I I sown S'OzNH-O OH NH; HO

' 0H 1 I 11.-- N: r brown N=NC\ olive.

C=N HS N02 i l sown,

As will be evident from the preceding table, the ogo'- dihydroxy-monoazo-dyestuffs (11), are made up front an o-hydroxydiazo-coinpound of tliebenzene series and, as coupling component, a compound Which-e. g. as in items 3 to 11 of the table-coupl'e's in the adjacent or vicinal position to a hydroxylgroup, or'a compound which--e. g. v

as in items 1 and 2 of the table -includes an acetoacetic acid anilide radical and couples in a-position relatively to the anilide group.

benzene-4-sulfonic acid isopropy lamide and acetoacetanilide. After the addition of a solution of 1.55 parts of cobalt sulfate, 1.55 parts of tartaric acid and 4 parts of sodium hydroxide in 100 parts of water, the whole is heated to 80-85 C. until the metallization is complete, whereby a solution results. Afterco'olin'g to room temperamre, a difficultly soluble compound is filteredofi. The filtrate is neutralized with acetic acidsandthe sep- .arafd dyestufiisolated by filtration, washed with dilute sodium chloride solution and dried; l-t'fo'rms a green powder which is soluble inwater with a g'reencolor and in concentrated sulfuric acid with a brown'coloryit dyes *wool from a weakly alkaline, neutral or acetic acid bath in full, uniform green tints of good fastness properties.

Example 3 2 parts of the cobaltiferous dyestu ff obtained according to paragraph 1 of Example 1 are dissolved in 4000 parts :c'f water, 2 parts of 40% aceticacid or 4 parts of ammonium acetate are added and 100 parts of well wetted 7 W001 are entered at 40-50 C. into the resulting dye bath. The bath is brought to the boil within /2 hour and i dyeing conducted at the boil for hour. The wool is finally rinsed with cold water and dried. The wool is dyed in green tints of good fastness fro-light and washing.

Similar dyeings are obtained by dyeing without the addition of acetic acid or ammonium acetate or by using u while the other contains as single water-s olubilizing group a member selected from the class consisting of a sulfonamide group and a sulfone group and corresponds to the formula 1 wherein R represents a benzene radical bound to the azo linkage in vicinal position to the OH grcmp and A represents a member selected from the group consisting of the radical of an acetoacetic acid anilide bound to the azo linkage in a-position relatively to the anilide group, the 2-hydroxynaphthalene, the 5,8 dichloro-l-hydroxynaphthalene and the 1-phenyl-3-methyl-5-pyrazolone-sulfonamide radicals bound to the azo linkage in vicinal position to their respective hydroxy group.

2. A complex cobalt compound which contains one atom of cobalt in complex'combination with substantially two molecules of diiferent monoazo-dyestufls of which one corresponds to the formula OH NH:

N=N DIN and the other corresponds to the 'tormula wherein R represents a benzene radical free from water xatom'of cobalt in complex combination with substantially two molecules of difierent monazo-dyestufis of which one corresponds to the formula "and the other corresponds to the formula SO CH3 wherein R represents a benzene radical free from water solubilizing substituents.

4. A complex cobalt compound which contains one atom of cobalt in complex combination with substantially two -molecules of difierent monoazo-dyestutfs of which one corresponds to the formula and the other corresponds to the formula wherein R represents a benzene radical free from water solubilizing substituents and bound to the OH group in vicinal position of the azo linkage, and Y represents a sulfonic acid amide group.

5. A complex cobalt compound which contains one atom of cobalt in complex combination with substantially two molecules of diiferent monoazo-dyestutts of which one corresponds to the formula and the other corresponds to the formula mulae 0H NH:

Wo g

and

7. The complex cobalt compound containing one atom of cobalt bound in complex union with one molecule of each of the monoazo-dyestuflFs corresponding to the formulae and 8. The complex cobalt compound containing one atom of cobalt bound in complex union with one molecule of each of the monazo-dyestufis corresponding to the formulae 0H NH:

' cm I and O 0 CH: C1 Nae-cg o O-NH Bot-CH3 9. The complex cobalt compound containing one atom of cobalt found in complex union with one molecule 10 of each of the monoazo-dyestufi's corresponding to the formulae and and

(|)H H0 01 U SO3-N113 1 References Cited in the file of this patent UNITED STATES PATENTS 2,551,056 Schetty May 1, 1951 2,565,898 Widmer et al. Aug. 28, 1951 2,674,515 Widmer et al. Apr. 6, 1954 2,711,404 Schetty June 21, 1955 2,734,895 Zickendraht et al. Feb. 14, 1956 2,749,332 Buehler et al. June'S, 1956 2,766,230 Buehler et al. Oct. 9, 1956 

1. A COMPLEX COBALT COMPOUND WHICH CONTAINS ONE ATOM OF COBALT IN COMPLEX COMBINATION WITH SUBSTANTIALLY TWO MOLECULES OF DIFFERENT MONAZO-DYESTUFFS OF WHICH ONE CORRESPONDS TO THE FORMULA 